Luận án tiến sĩ hóa học nghiên cứu tổng hợp một số pheromone côn trùng dạng alcohol chứa nhóm methyl liền kề và (z) alken 1 ol

BỘ GIÁO DỤC VÀ ĐÀO TẠO VIỆN HÀN LÂM KHOA HỌC VÀ CÔNG NGHỆ VIỆT NAM HỌC VIỆN KHOA HỌC VÀ CÔNG NGHỆ - NCS LÊ VĂN DŨNG NGHIÊN CỨU TỔNG HỢP MỘT SỐ PHEROMONE CÔN TRÙNG DẠNG ALCOHOL CHỨA NHÓM METHYL LIỀN KỀ VÀ (Z)-ALKEN-1-OL LUẬN ÁN TIẾN SĨ HÓA HỌC Tp HCM – Năm 2023 BỘ GIÁO DỤC VÀ ĐÀO TẠO VIỆN HÀN LÂM KHOA HỌC VÀ CÔNG NGHỆ VIỆT NAM HỌC VIỆN KHOA HỌC VÀ CÔNG NGHỆ - LÊ VĂN DŨNG NGHIÊN CỨU TỔNG HỢP MỘT SỐ PHEROMONE CÔN TRÙNG DẠNG ALCOHOL CHỨA NHÓM METHYL LIỀN KỀ VÀ (Z)-ALKEN-1-OL Chuyên ngành: Hóa hữu Mã sỗ: 9.44.01.14 LUẬN ÁN TIẾN SĨ HÓA HỌC NGƯỜI HƯỚNG DẪN KHOA HỌC: PGS TS ĐẶNG CHÍ HIỀN GS TSKH NGUYỄN CƠNG HÀO TP HCM – 2023 LỜI CẢM ƠN - -Trước hết, xin cảm ơn Học viện Khoa học Công nghệ, Viện Hàn lâm Khoa học Công nghệ Việt Nam tạo điều kiện thuận lợi để tơi hồn thành luận án tiến sĩ Tơi xin chân thành cảm ơn đến PGS.TS Đặng Chí Hiền GS TSKH Nguyễn Công Hào quý thầy cô Viện Cơng nghệ Hóa học truyền đạt kiến thức, hướng dẫn tận tình, tạo điều kiện cho tơi suốt thời gian thực đề tài nghiên cứu Tôi xin chân thành cảm ơn TS Nguyễn Hồng Ửng, Khoa Nông nghiệp trường Đại học Trà Vinh tư vấn giúp nhiều kiến thức giá trị thử nghiệm sinh học đồng ruộng Tôi xin chân thành cảm ơn Ban giám hiệu, tất quý thầy cô Trường THPT Diệp Minh Châu nhiệt tình hỗ trợ tơi q trình học tập nghiên cứu Tơi cảm ơn bạn sinh viên, bạn học viên cao học, bạn nghiên cứu sinh động viên, chia q trình tơi thực đề tài Cảm ơn tất người thân gia đình ln động viên tinh thần để giúp tơi hồn thành luận án Xin chân thành cảm ơn! Thành phố Hồ Chí Minh, năm 2023 Nghiên cứu sinh Lê Văn Dũng LỜI CAM ĐOAN Luận án Tiến sĩ Hóa học: “Nghiên cứu tổng hợp số pheromone côn trùng dạng alcohol chứa nhóm methyl liền kề (Z)-alken-1-ol” tơi thực hiện, số liệu, kết trung thực Thành phố Hồ Chí Minh, năm 2023 Nghiên cứu sinh Lê Văn Dũng MỤC LỤC MỤC LỤC DANH MỤC CÁC KÝ HIỆU, CÁC CHỮ VIẾT TẮT DANH MỤC CÁC BẢNG - DANH MỤC CÁC HÌNH DANH MỤC CÁC SƠ ĐỒ - MỞ ĐẦU CHƯƠNG TỔNG QUAN - 11 1.1 Giới thiệu pheromone 11 1.1.1 Định nghĩa pheromone 11 1.1.2 Đặc điểm phân loại pheromone 11 1.1.3 Các dạng cấu trúc pheromone thường gặp 13 1.2 Giới thiệu số pheromone côn trùng Việt Nam 15 1.2.1 Đuông dừa 15 1.2.2 Bọ xít muỗi 17 1.2.3 Sâu tơ 18 1.2.4 Bọ hà khoai lang 22 1.2.5 Sâu keo mùa thu 24 1.3 Tổng quan vấn đề nghiên cứu 27 1.3.1 Tổng hợp số hợp chất racemic alcohol bậc chứa nhóm methyl liền kề 27 1.3.2 Tổng hợp hợp chất chứa nối đôi (Z)-alken-1-ol 29 CHƯƠNG NGHIÊN CỨU 36 2.1 Nội dung nghiên cứu 37 2.1.1 Tổng hợp thử nghiệm alcohol bậc chứa nhóm methyl liền kề theo quy tắc Cram xác định cấu trúc (tỷ lệ đồng phân cấu hình threo : erythro) phổ NMR 37 2.1.2 Tổng hợp số pheromone côn trùng (Z)-alken-1-ol, ester (Z)-alken-1-ol thử nghiệm chọn lọc đồng ruộng 38 2.2 Phương pháp nghiên cứu 39 2.2.1 Phương pháp xác định cấu trúc 39 2.2.2 Phương pháp xác định số vật lý 40 2.2.3 Phương pháp tổng hợp alcohol bậc chứa nhóm methyl liền kề theo quy tắc Cram 40 2.2.4 Phương pháp tổng hợp pheromone dạng (Z)-alken-1-ol ester 46 2.3 Thực nghiệm 63 2.3.1 Hóa chất thiết bị 63 2.3.2 Tinh chế chất 65 2.3.3 Quy trình tổng hợp chất 66 CHƯƠNG KẾT QUẢ VÀ THẢO LUẬN - 85 3.1 Tổng hợp pheromone alcohol bậc chứa nhóm methyl liền kề 85 3.1.1 Kết tổng hợp pheromone alcohol bậc chứa nhóm methyl liền kề phản ứng Grignard theo quy tắc Cram đánh giá tỷ lệ đồng phân cấu hình threo : erythro sản phẩm alcohol (a) (b) 85 3.1.2 Phản ứng oxi hóa alcohol bậc chứa nhóm methyl liền kề thành ketone 91 3.1.3 Hoàn nguyên ketone (1c-15c) LiAlH4/ether 92 3.2 Tổng hợp pheromone (Z)-alken-1-ol ester 95 3.2.1 Kết tổng hợp n-bromoalkan-1-ol từ diol 95 3.2.2 Phương pháp khử alkyne thành (Z)-alkene mà không sử dụng hydrogen phân tử 96 3.3 Thử nghiệm sinh học 108 3.3.1 Kết thử nghiệm pheromone alcohol bậc chứa nhóm methyl liền kề108 3.3.2 Kết thử nghiệm với pheromone dạng (Z)-alken-1-ol 116 KẾT LUẬN 121 KIẾN NGHỊ - 123 DANH MỤC CÁC CƠNG TRÌNH CỦA TÁC GIẢ 124 TÀI LIỆU THAM KHẢO - 126 PHỤ LỤC 141 DANH MỤC CÁC KÝ HIỆU, CÁC CHỮ VIẾT TẮT KÍ hiệu Tiếng Anh Ald Chemical shift Ac2O Acetic anhydride 13 Carbon Nuclear Magnetic Resonance C-NMR -CH2- Methylene CDCl3 Deuterated chloroform (C6H5)3P Triphenylphosphine ChCl Choline choride CH3- Methyl C2H5- Ethyl C3H7- n-Propyl C4H9- n-Butyl C5H11- n-Pentyl C6H13- n-Hexyl C7H15- n-Heptyl C8H17- n-Octyl CH3- Methyl C2H5- Ethyl C3H7- n-Propyl d Tiếng Việt Độ dịch chuyển hóa học Cộng hưởng từ hạt nhân carbon Tỷ trọng DMSO Dimethyl sulfoxide DEPT Distortionless Enhancement Phổ DEPT d Doublet Mũi đôi dd doublet of doublet Mũi đôi đôi DES Deep eutectic solvent Dung môi sâu DHP 3,4-Dihydropyran DMM Dimethoxymethane EtOAc Ethyl acetate EtOH Ethanol EO Ethylen oxide (E) Entgegen GC-MS Gas Chromatography-Mass Spectrometry Proton Nuclear Magnetic Resonance H-NMR h Hour IBX 2-Iodoxybenzoic acid J Coupling constant  Micro MW Microwave MeOH Methanol m n-BuLi Multiplet Khác bên Cộng hưởng từ hạt nhân proton Giờ Hằng số ghép Lị vi sóng Mũi đa n-Butyllithium NT Nghiệm thức Nu: Nucleophile OAc Acetate ppm Part per million pTSA p-Toluenesulfonide acid Py Pyridine PdNPs Palladium nanoparticles PEG Poly(ethylene glycol) Pd(dba)2 Bis(dibenzylideneacetone)palladium (0) PCC Pyridinium chlorochromate PPTS Pyridinium p-toluenesulfonate s Singlet Phần triệu Mũi đơn Sùng khoai lang SKL t Triplet THF Tetrahydrofuran THP Tetrahydropyran TLC Thin liquid chromatography (Z) Zusamment Mũi ba Cùng bên DANH MỤC CÁC BẢNG Bảng 2.1 Khảo sát tỷ lệ đồng phân threo:erythro alcohol (a) (b) 42 Bảng 2.2 Khảo sát điều kiện phản ứng oxi hóa alcohol IBX 44 Bảng 2.3 Oxi hóa alcohol (a) thành ketone (c) 44 Bảng 2.4 Khảo sát tỉ lệ đồng phân threo:erythro alcohol (d) 45 Bảng 2.5 Khảo sát điều kiện phản ứng khử 3-hexyn-1-yl tetrahydropyran-2yl ether (1) thành (Z)-3-hexen-1-yl tetrahydropyran-2-yl ether (2) 48 Bảng 2.8 Các nghiệm thức khảo sát hiệu dẫn dụ pheromone giới tính liều lượng/ bẫy khác bọ hà khoai lang đồng ruộng 60 Bảng 2.9 Khảo sát hiệu dẫn dụ pheromone giới tính theo thời gian bọ hà khoai lang 61 Bảng 2.10 Các nghiệm thức khảo sát ảnh hưởng độ cao đặt bẫy khả dẫn dụ bọ hà khoai lang đồng 62 Bảng 2.11 Các nghiệm thức khảo sát ảnh hưởng kiểu vật liệu bẫy khả dẫn dụ bọ hà khoai lang ruộng khoai lang 62 Bảng 3.1 Độ dời hóa học H C -CHOH alcohol 1a-15a 86 Bảng 3.2 Độ dời hóa học H C -CHOH alcohol 1b-15b 89 Bảng 3.3 Kết tỷ lệ đồng phân threo : erythro alcohol 1a-15a 1b15b 90 Bảng 3.4 Kết khảo sát phản ứng oxi hóa (±)-4-methyl-5-nonanol (10a) IBX 91 Bảng 3.5 Kết độ dời hóa học H -CHOH tỷ lệ phân threo : erythro alcohol 1d-15d 93 Bảng 3.6 Kết khảo sát tổng hợp n-bromoalkan-1ol từ diol 96 Bảng 3.7 Kết khảo sát ảnh hưởng hệ xúc tác palladium đến phản ứng khử 3-hexyn-1-yl tetrahydropyran-2-yl ether 97 Bảng 3.8 Kết thử nghiệm ban đầu alcohol 1b-15b ketone 1c-15c 113 Bảng 3.9 Kết ảnh hưởng kiểu vật liệu chế tạo bẫy lên hấp dẫn pheromone 120 DANH MỤC CÁC HÌNH Hình 1.1 Mơ tả phương thức giao tiếp hai cá thể lồi 11 Hình 1.2 Đng dừa trưởng thành 15 Hình 1.3 Bọ xít muỗi 17 Hình 1.4 Sâu tơ 18 Hình 1.5 Bọ hà khoai lang 22 Hình 1.6 Sâu keo mùa thu 24 Hình 2.1 Phản ứng cộng magnesium vào hợp chất aldehyde 40 Hình 2.2 Bẫy đng dừa 55 Hình 2.3 Địa điểm phương pháp đặt bẫy đuông dừa 55 Hình 2.4 Bẫy bọ hà khoai lang 58 Hình 2.5 Mồi nhử bọ hà khoai lang 58 Hình 2.6 Địa điểm phương pháp đặt bẫy pheromone 59 Hình 3.1 Tỉ lệ hỗn hợp đồng phân threo : erythro alcohol (15a), (15b) 91 Hình 3.2 Có chế ion hydride cộng vào nhóm carbonyl 93 Hình 3.3 Cơ chế khử alkyne thành cis-alkene với hệ xúc tác Pd(dba)2/KOH/DMF 98 Hình 3.4 Hai proton H -CH=CH- phổ 1H NMR (Z)-3-hexen-1-yl tetrahydropyran-2-yl ether 99 Hình 3.5 Hai proton H -CH=CH- phổ 1H NMR (Z)-3-hexen-1-ol 102 Hình 3.6 Hai proton H -CH=CH- phổ 1H NMR (Z)-3-dodecen-1-ol 105 Hình 3.7 Bốn proton HA, HB, HC, HD hợp chất (11C) 106 Hình 3.8 Hằng số ghép cặp hai proton HA, HB hợp chất (11C) 106 Hình 3.9 Hằng số ghép cặp hai proton HC, HD hợp chất (11C) 107 Hình 3.10 Trung bình số trùng vào bẫy NT1 đến NT3 109 Hình 3.11 Số lượng côn trùng vào bẫy NT4 đến NT7 111 Hình 3.12 Trung bình số đng dừa vào bẫy hợp chất (4a), (4c), (5c), (10a), (10b), (11a), (11b), (11c) tổ hợp (11a + 11c), (11b + 11c) 114 Hình 3.14 Kết thử nghiệm bọ hà khoai lang liều lượng khác 117 Hình 3.15 Kết khảo sát bẫy mồi nhử bọ hà khoai lang theo thời gian 118 126 TÀI LIỆU THAM KHẢO [1] N C Hào, Những khả biện pháp phịng trừ sâu bệnh khơng gây nhiễm môi sinh, Nhà xuất nông nghiệp, 1997, Thành Phố Hồ Chí Minh [2] B C Hiển, Pheromon trùng, Nhà xuất Khoa học Kỹ Thuật Hà Nội, 2002, 13-16 [3] B C Hiển, Pheromon côn 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